N-hydrocarbon substituted alkanol



Patentedoct. 2, 1945 Fred L. Chappell, Jr.,Kalamazoo, Mich., assignor to Hercules Powder Company, Wilmington, Del., a corporation of Delaware No Drawing. Application April 24, 1941,

Serial No. 390,113

' 19 Claims. (Cl. 106-144) This inventionrelates to paper sizing compositions, and in particular concerns aqueous rosin size dispersions in which a high proportion of the rosin is in free iorm.

In the manufacture of papers requiring resistance to water and ink penetration, it has long been common practice to size such' papers by treating the paper pulp in the beating engine with an aqueous solution or dispersion of partially or completely saponified rosin. The pulp so treated is then further treated with an aqueous which, take place during such sizing operation,

' but at the present time it is the general belief that there is formed a iioc of aluminum reslnate, free rosin, and alumina which adheres to the.

pulp fibers, and upon subsequent sheeting andvarious advantages not specifically referred to' herein will occur to thoseskilled in the art up n employment of the invention in-practice.

In accordance with the above and related objects, I have found that substantially non flocking high free rosin size dispersions may be prepared by treating the ordinary partially or com- I pletely saponified rosin size dispersions with an organic acid anhydride. These acid materials react with the saponifled rosin to form a relatively stable emulsion or dispersion of free rosin containing'a dissolved salt of the corresponding organic acid. Such salt serves as a bufiering agent. The dispersion so formed is preferably,

drying of the same imparts thereto'a lasting degree of resistance to water and ink penetration.

In localities where hard water conditions prevail, i. e.,: where water containing considerable amounts of dissolved calcium and magnesium salts is used for diluting the pulp in-the beating engine, however, considerable dlmculty is experifurnish. Flocking in the presence of hard water has to some degree been overcome by the use of rosin size dispersions in which a high proportion although not necessarily, further stabilized with a proteinaceous protective colloid. The rosin dispersions prepared in this manner are characterized by extremely small particle size, in some cases almost beyond the range of microscopic visibility, and accordingly have excellent stability to 11001:- ing in the presence of hard water and possess exceptio'nal sizing'value. Furthermore, since a large proportion, e. 8., 50-100 percent by weight, of the rosin is in free form, a minimum of alum is'required to precipitate the size on the-pulp fibers. The aqueous saponified rosin dispersions which are treated with an organic acid anhydride ac-- cording to the invention may be prepared from partially saponlfled rosin containing from 15 to 40 percent or more of free-rosin, or they may be prepared from completely saponifled rosin,-such as the commercially-available dry rosin size. Or-

of the rosin'is in free, i.'e., unsaponifled, Iorm.

Such dispersions are usually prepared with the aid ore protective colloid such'as casein or veg-. et'able protein, and while certain of, such sizes have enjoyed moderate commercial usage, they still leave much to be'desired with respect to flocking in the presence of hard water.

It is accordingly an object 01 this invention to --'provide aqueous rosin size dispersions which dis-' dispersions dina'rily it will be round preferable to, employ gree of saponiflcatlon. The saponifled rosin so,

prepared is then, dispersed in water by simple dilution or with the aid of a suitable emulsifying device to form a homogeneous dispersion'or emulsion containing from about 1 to about 25 percent by weight of solids prior to treatment with the acid anhydride.

Any organic acid anhydride which is sum-' ciently acidin aqueous solution to saponlfled rosin, e. g., acetic anhydride, malelc g, ..;andj auhydride, phthalic anhydride, succinic sullyanhydride in place of the maleic anhydride. The I dispersion so prepared had excellent stabilityto hard water flocking. I

Example VI employed in an amount insufilcient to reduce the 1 DH of the dispersion below about 6.

6. In a method of making a high free rosinslze dispersion, the steps which comprise forming a dilute aqueous dispersion of at least partially'saponified rosin,-said rosin having been saponified by means of an alkali metal alkali, stabilizing said dispersion by the addition of an amount of casein vention may be employed instead 01' those explained, change being made as regards the methods or ingredients herein disclosed, provided the method stated by any'of the following claims be employed or the product defined by any or said claims be obtained.

What I claim and desire to protect by Letters Patent is:

1. In a method of making a high free rosin size dispersion, the steps which comprise forming adilute aqueous dispersion of at least partially saponified rosin, said rosin having been saponified by means of an alkali metal alkali, stabilizing said dispersion by the addition of a proteinaceous protectiye colloid, and thereafter treating the stabilized dispersion with an organic acid anhydride capable of hydrolyzing said saponified rosin in aqueous solution, said organic acid anhydride being employed in an amount insufilcient to reduce the pH of the dispersion below about 6. f

2. In a method of making a high free rosin size dispersion, the steps which comprise forming a dilute aqueous dispersion of at leastpartially saponified rosin, said rosin having been saponified by means of an alkali metal alkali, stabilizing said I dispersion by the addition of casein, and thereafter treating the stabilized dispersion with an organic acid anhydride capable of hydrolyzing said saponified rosin in aqueous solution, said organic acid anhydride being employed in an amount insumcient to reduce the pH of the dispersion below about 6.

3. In a method of making a high free rosinsize dispresion, the steps which comprise forming a dilute aqueous dispersion of at least partially saponified rosin, said rosin having been saponified by means of an alkali metal alkali, stabilizing said dispersion by the addition of casein, and

thereafter treating the stabilized dispersion with phthalic anhydride in an amount insufflcient to reduce the pH of the dispersion below about 6.

4. In a method of making a high free rosin size dispersion, the steps which comprise forming a dilute aqueous dispersion of substantially completely saponified rosin, said rosin having been saponified by means or an alkali metal alkali,'stabilizing said dispersion by the addition of sodium caseinate, and thereafter treating the stabilized dispersion with phthalic anhydride-in an amount insufficient to reduce the pH of the dispersion below about 6.

5. In a methodof making a high free rosin size dispersion, the steps which comprise forming a dilute aqueous dispersion" of at least partially saponified rosin, said rosin having been saponified by means of an alkali metal alkali stabilizing said dispersion by the addition or an amount of a proteinaceous protective colloid representing between about 5 and about 20 percent of the weight of the saponified rosin, and thereafter treatin the stabilized dispersion at ,a temperature below,

' ous solution, said organic acid anhydride being after treating the stabilized dispersion at a temperature below about 60 C. with an amount of phthalic anhydride insufiicient to reduce the pH of the dispersion below about 6.

"7. In a method of making a high free rosin size dispersion,- the steps which comprise forming a dilute aqueous dispersion of substantially completely saponified rosin, said rosin having been saponified by means of an alkali metal alkali, stabilizing said dispersion by the addition of an amount of sodium caseinate representing between about 5 and about 20 percent by weight of the saponified rosin, and thereafter treating the stabilized dispersion at a temperature below about 60 C. with an amount of pht'haiic anhydride representing between about 6 and about 12 percent by weight of the saponified rosin.

8. A method of making a high free rosin size dispersion which comprises treating an aqueous dispersion comprising saponified rosin, said rosin having been saponified by-means of an alkali metal alkali, with an organic acid anhydride capable of hydrolyzing said sapomfied rosin in aqueous solution, said organic acid anhydride being employed in an amount insufficient to reduce the pH of the dispersion below about 6.

9. A method .of making a high free rosin size dispersion which comprises treating an aqueous dispersion comprising saponified rosin, said rosin having been saponified by means of an alkali metal alkali, and said dispersion'having been 10. A method or making a high free rosin size dispersion which comprises treating an aqueous dispersion comprising saponified rosin, said rosin having been saponified by means of 'an-alkali metal alkali, and said dispersion having been stabilized with casein, with an organic acid anhydridev capable of hydrolyzing said saponified rosin in aqueous solution, said organic acid anhydride being employed in an amount of at least 3 percent of the weight of saponified rosin but in an amount insufl icient to reduce the pH of the dispersion below about 6. i

11. A method of making a high free rosin size dispersion which comprises treating an aqueous dispersion comprising saponified'rosin, said rosin having been saponified by means or an alkali metal alkali, and said dispersion having been stabilized with a proteinaceous protective colloid, with-phthalic anhydridepresent in an amount of at least 3 percent of the weight of saponified rosin but in an amount insufllcient to reduce the pH 01 the dispersion below about 6. I

. 12. A method ofmaking a high free rosin size dispersion which comprises treating an aqueous dispersion comprising saponified rosin, said rosin having been saponified by means or, an alkali metal alkali, and said dispersion having been stabilized with casein, with phthalic anhydride present in an amount of at least 3 percent of the weight of saponified rosin but inan' amount in: v

pH of the dispersion below with maieic anhydride present in an amount of at least 3 percent the weight of saponified rosin but in an amount insufficient to reduce the pH of the dispersion below about 6.

17. A method of making a high free rosin size dispersion which comprises'treating an aqueous dispersion comprising saponified rosin, said rosin 14. A method of making a high freerosin size dispersion which comprises treating an aqueous dispersion-comprising saponified rosin, said rosin having been saponified by means of an alkali .metal alkali, with maleic anhydride, said maleic anhydride being employed in an amount insufi'lcient to reduce the pH 'of the dispersion below about 6. a

15. A method of making a high free rosin size dispersion which comprises treatingan aqueous dispersion comprising saponified rosin, said rosin having been saponified by means of an alkali metal alkali, with terpinene-maleic anhydride,

said terpinene-maleic anhydride being employed in an amount insufiicient to reduce the pH of the dispersion below about 6.

. 16. A method of making a high freerosin size dispersion which comprises treating an aqueous dispersion comprising saponifled rosin, said rosin having been; saponified by means of an alkali metal alkali, and said dispersion having been stabilized with a proteinaceous protective colloid,

having been saponified by means of an alkali metal alkali, and said dispersion having been stabilized with a proteinaceous protective colloid, with terpinene maleic anhydride present in an amount of at least 3 percent of the weight of saponified rosin but in an amount insuflicient toreduce the pH of the dispersion below about 6.

18. A method of making a high free rosin size dispersion which comprises treating an aqueous dispersion comprising saponified rosin, said rosin having been saponified by means of an alkali metal alkali, and said dispersion having been stabilized with casein, with m'aleic anhydride present in an amount of at least 3 per cent of the weight of saponified rosin but-in an amountinsufiicient to reduce the pH of the dispersion below about 6. 19. A method of making a high free rosin size dispersion which comprises treating-an aqueous dispersion comprising saponified rosin, said rosin insufiicient to reduce the pH of the dispersion be low about 6.

FRED, L. CHAPPELL, JR.

Patented Oct. 2, 1945 N-HYDROCARBON SUBSTITUTED ALKANOL- AMINE SALTS OF DINITBO-PHENOLS Gerald B. Coleman and Frank B. Smith, Midland,

Mich, aasignors to The Dow Chemical Company, Midland, Mich, a corporation of Michi- No Drawing. Application April 25, 1941, Serial No. 390,367

6 Claims.

This invention relates to amine salts of phenols, and is particularly concerned with the addition products of dinitro-phenols with N-hydrocarbon-substituted alkanolamines having the following formula:

a wherein R. represents alkyl, cycloalkyl, or aralkyl, R represents alkyl, cycloalkyl, aralkyl, hydroxyalkyl, or hydrogen, and n is an integer, and to parasiticidal composition comprising such amine salts as active toxicants. We have prepared representative members of the above-identified group of compounds and found them for the most part to be crystalline solids, somewhat soluble in many common organic solvents. These compounds ar stable to light and air, not appreciably affected by carbon dioxide, and are yellow to orange-red in color. A preferred group of amine salts are obtained from those dinitro-phenols characterized by nuclear-substituted nitro groups in the para position and in one of the positions ortho to the hydroxyl.

A group of compounds falling within the scope of the invention as defined above which are particularly valuable for use in insecticidal and fungicidal spray and dust compositions because of their relatively low water solubility are those N-hydrocarbon-substituted alkanolamine salts derived from 2.4-dinitro-phenols having the formula:

. etc. with a solution of a dinitro-phenol in benzene, chlorobenzene, or alcohol. Substantially equimolecular proportions of nitro-phenol and amine have been found to give the desired salts in good yield, although any suitable amounts may be employed. Where an excess of one or the other reactant is present in the final product, separation is readily accomplished by extraction as with benezene or other selective solvents for the nitro-phenoi and amine in which the amine salt is more diflicultly soluble. The operating temperatures are not critical, although reduced amounts of solvent are required when the reaction is carried out at somewhat elevated temperatures, e. g. between about 40 and 120 C. The reaction can be conveniently carried out at any desired temperature up to the refluxing temperature of the reaction mixture. While'the reactants and solvent may simply be mixed together, a convenient method of operation comprises adding a solution of one reactant to a solution of the other. To insure the formation oi a relatively homogeneous product and to minimize occlusion, the amine solution is preferably added portionwise with stirring to a solution of the phenol over a short period of time. Following completion of the reaction, the mixture is filtered or otherwise manipulated to separate out th insoluble amine salt which may be further purified by washing with small amounts of such. solvents as benezene,- chlorobenzene, petroleum ether, and the like. The amine salt obtained as a residue from the separation is then dried at a temperature calculated to volatilize residual traces of solvent.

The following examples set forth certain embodiments of the invention but are not to be construed as limiting the same:

Example 1 26.6 grams (0.1 mole) of 2.4-dinitro-6-cyc1o hexyl-phenol and 50 milliliters of benzene were mixed together and warmed to approximately 78 0., at which temperature the phenol was entirely dissolved in the benzene. 13.3 grams (0.1 mole) of N-ethyl-diethanolamine dissolved in 10 milliliters of methanol was then added portionwise to the phenol solution over a period of approximately 15 minutes. The reaction solution was heated and stirred for a short time and thereafter cooled whereupon the crude amine salt precipitated from solution. The mixture was then filtered, and the residue of amine salt washed with cold benzene and air-dried, whereby there was obtained 32 grams of the N-ethyldiethanolamine salt of 2.4-dinitro-6-cyclohexylphenol as a light yellow crystalline compound melting at 84-86 C. This salt was somewhat soluble in per cent ethanol and substantially oil. A saturated water solution at'26 C. contained 1.53 per cent by weight of the compound and had a-pH of 8.1.

Example 2 Similarly, a solution of 53.2 grams (0.2 mole) of 2.4-dinitro-6-cyclohexyl-phenol in'20 milliliters of boiling benzene was reacted with a solution of 23.4 grams (0.2 mole) of N.N-diethyl- -ethanolamine in 20 milliliters of hot methanol.

After all of the amine solution had been stirred into the reaction mixture, heating and stirring were continued for a short period. The mixture was then cooled and filtered to obtain a crude amine addition salt as a residue. This residue was recrystallized from 150 milliliters of chlorobenzene and dried under vacuum, whereby there was obtained 55 grams of the N.N-diethylethanolamine salt of 2.4-dinitro-6-cyclohexylphenol as a bright yellow crystalline solid, melting at 70-72 C. This compound was somewhat soluble in ethyl alcohol and hot carbon tetrachloride, and substantially insoluble in petroleum oil. A saturated water solution at 26C. contained 0.5 per cent by weight of the compound and had a pH of 7.6.

Example 3 26.6 grams (0.1 mole) of 2.4-dinitro-6-cyclohexylphenol and 8.9 grams (0.1 mole) of N-ethylmonoethanolamine were reacted together in 120 milliliters of hot benzene substantially as described in the foregoing examples. 34.5 grams of the N-ethyl-monoethanolamine salt of 2.4-dinitro-G-cyclohexyl-phenol was thereby obtained as an orange crystalline compound melting at 123-125.5 C. This compound was somewhat soluble in ethyl alcohol and hot carbon tetra-' chloride, and substantially insoluble in petroleum distillate. A saturated water solutioi at 26 C. contained 0.47 per cent by weight of the compound and had a pH of 7.6.

Example 4 18.4 grams (0.1 mole) of 2.4-dinitro-phenol, 16.1 grams (0.1 mole) of N-butyl-diethanolamine, and 5 milliliters of benzene were mixed together. Considerable heat of reaction was immediately evolved. The mixture was warmed on a hot plate with stirring and thereafter cooled to approximately to obtain a solid reaction product consisting essentially of the amine addition salt.

This product was successively dispersed in petroleum ether and benzene and thereafter airdried to obtain 33.5 grams of the N-butyl diethanolamine salt of 2.4-dinitro-phenol as a yellow crystalline compound melting at 60-62 C. This compound is very soluble in water. A saturated aqueous solution at 26 C. contained 90.36 pe9r cent by weight of the salt and had a pH of 6.

Example Ina/similar manner 15.9 grams of 2.4-dinitro- 6-ethyl-phenol and 12.1 grams of N-butyl-diethanolamine were reacted together in the presence of 20 grams of benzene 'to obtain an oily product which solidified on standing. This crude product was recrystallized from a mixture of ethyl alcohol and benzene to obtain 20 grams of N-butyl-diethanolamine salt of 2.4-dinitro-6- ethyl-phenol as yellow crystals melting at 81-82 C. A saturated water solution at 26 C. con- 1 2 2,885,795 3 insoluble in carbon tetrachloride and petroleum tained 3.65 per cent by weight of the compound and had a pH of 6.6.

Example li 19.8 grams (0.1 mole) of 2.4-dinitro-6-methylphenol and 17.3 grams (0.1 mole) of N.N.-dibutylethanolamine were mixed together'in 30 milliliters of benzene with heating and stirring. milliliters of petroleum ether .(boiling point -100 C.) was added to the 'warm reaction mixture, .whereby an oily product precipitated. This oil was separated and cooled to approximately 0 C., whereupon th crude amine addition salt product crystallized. The crude product .was washed with petroleum ether and air-dried,

whereby .there was obtained 34 grams of N.N- dibutyl-ethanolamine salt of 2.4-dinitro-6- methyl-phenol as a yellow crystalline compound melting at 59-60f C. A saturated water solution at 26? C. contained 1.354 per cent by weight of this compound and had a pH of 6.4.

Example 7 26.6 grams (0.1 mole)' of 2.4-dinitro-6-cyclohexyl-phenol was dissolved in 30. milliliters of benzene. and 11.7 grams (0.1 mole) of N-butylmonoethanolamine dissolved in 20 milliliters of benzene added thereto. The reaction mixture was warmed to its boiling temperature for several minutes with stirring and thereafter cooled, whereupon the amine addition salt of the phenol crystallized from solution. The resulting mixture was filtered, and the residue recrystallized from benzene and air-dried to obtain 31.5 grams of the N-butyl-monoethanolamine salt of 2.4-dinitro-6- cyclohexyl-phenol as an orange crystalline compound melting at 99.5-102 C. This compound is slightly soluble in ethanol and hot carbon tetrachloride, and substantially insoluble in petroleum distillate. A saturated water solution at 26 C. contained 0.19 per cent by weight of the compound and had a pH of 7.3.

Example 8 14.3 grams (0.1 mole) of N-cyclohexyl-monoethanolamine, 26.6 grams (0.1 mole) of 2.4-dinitro-fi-cyclohexyl-phenol, and 30 milliliters of benzene were mixed together and warmed on a steam bath for 1 hour. The reaction mixture was then cooled and filtered, whereby there was obtained 26 grams of the N-cyclohexyl-monoethanolamine salt of 2.4-dinitro-6-cyclohexylphenol as an orange crystalline compound melting at 132-135 C. A saturated water solution at 26 C. contained 0.15 per cent by weight of the compound and had a pH of 7.2.

Example 9 8.7 grams (0.038 mole) of 2.4-dinitro-6-cyclohexylphenol and 7.3 grams (0.038 mole) of N.N- di-(cyclohexyl) -ethanolamine were dispersed in a small amount of benzene and warmed for 1 hour on a steam bath. The reaction mixture was then cooled and filtered to obtain 12.5 grams of N.N-di- (cyclohexyl) -ethanolamine salt of 2.4-

dinitro-fi-cyclohexylphenol as a yellow crystalline compound melting at --142 C. when recrystallized from benzene. A saturated water solution at 26 0. contained 0.02 per cent by weight of this compound and had a pH of 6.3.

Other N-hydrocarbon substituted alkanolamines may be employed as shown in the examples to obtain addition salts of the dinitrophenols. Representative of such amine compounds are N-benzyl-monoethanolamine, N.N- dibenzylemonoethanolamine, N- (beta phenyl- 

